Olefin hydration process



Dec. 25, 1951 c, R NELSON ET AL 2,579,601.

OLEFIN HYDRATION PROCESS Filed Aug. 16, 1950 v TED/Q H3 P04 CURVEI 300C 5 o i CURVEIE 1 4 \Aoo 1.80 c

PKESSURE PouNus PER SQUARE INC-H .5 1.0 [.5 Lb 1.5 MOLE EA'HO -WATER VAPOR ETHYLENE lnverfl'ofs Charles 2. Nelson Marion A .D.Ta \Or Donald DkDavi son Lesfie M.Pe+ers BL; Their A'H'orneq Patented Dec. 25 1951 UNITED STATES PAT'ENT OFFICE OLEFIN HYDRATION PROCESS Charles R. Nelson, Orinda, Marion A. D. Taylor, Berkeley, Donald D. Davidson, Walnut Creek, and Leslie M. Peters, San Francisco, Calii'., assignors to Shell Development Company, San Francisco, Calif., a corporation of Delaware Application August 16, 1950, Serial No. 179,836 g I 13 Claims. (Cl. 260-441) g This invention relates to a process for the hy- I therefrom as the process continues. While the dration of olefins, and finds particular utility process is applicable to the hydration of any oleas applied t the direct hydration of ethylene to flii, it is particularly effective when employed in ethanol. T is application is a continuation-inthe hydration of ethylene or other normally part of our application Serial No. 770,392, filed gaseous ole'flns such as propylene or butylene. August 25, 1947, and now abandoned. Accordingly, the invention will be described While a number of processes for hydrating hereinafter as it relates to the hydration of such olefins to the corresponding alcohols are known, gaseous oleilns, and more particularly to the hythe majority thereof have drawbacks of one type dration of ethylene. I i 4 or another which seriously impair their utility. We have found that ethylene may be con- Thus, as regards ethylene, for example, the only verted to ethyl alcohol in an eflicient and ecohydration method heretofore employed on a nomical manner bycontinuously passing a heatcommercial scale has involved absorption of the ed, gaseous mixture of ethylene and water vapor, ethylene in sulfuric acid, followed by hydrolysis in suitable proportions and at an elevated presof the resultant ethyl sulfate, 9, process which is sure, through a catalyst bed comprisi Solid obviously undesirable insofar as it presents seriporous support which isincompletely saturated ous corrosion problems and involves high proc-- with an aqueous solution of phosphoric acid havessing and reactant costs. Accordingly, it would ing a strength f a l ast 70% and which is free be desirable if a hydration process for ethylene of substantially all seepage of the acid solution. and other oleiins were available which would Further amounts of an aqueous solution of free greatly reduce the corrosion factor and which at ph sph r c acid, r f rr d to h re n s refr sher the same time would be relatively economical of acid, are added to the bed as the process conoperation. tinues to make up for the losses of phosphoric It is therefore a general object of the present acid from the bed and so maintain the activity invention to provide an improved process for hyof the latter at a high level. Reaction temperadrating olefins to alcohols. A more particular tures between 270 and 310 C. are preferably object is to provide an eilicient and economical maintained in the bed, and the various condiprocess whereby ethylene and other olefins may tiOnS temperature, p s u and ratio of be directly hydrated to alcohols by passing a. t yl e to Wat r v por in the feed are so admixture of the gaseous olefin and water vapor l as o bring the acid in e b d to a 0 7 over a phosphoric acid catalyst, A further centration of at least 70% both on starting up ject is to provide a direct olefin hydration procthe process as well as afterthe addition of reess of this character wherein the corrosion face r ac d o m i t n t e a id c centor is greatly reduced. Still another object is tration in the bed'at 70%or above during u to provide an olefin hydration process of the Stflntialll' the entire ydration per od. foregoing type which may be carried out for h Solid pp f the Phosphoric a may I 'long periods of time at high eiiiciencywithout be m e p Of y Strong, Porous material having to shut down the unit in order to maini s d a s pt v t r aqu us p sp ic tain the activity of the catalyst at a high level. acid solutions, coupled with resistance to attack The nature of other objects of the invention will 40 by- While V i us S as, u as, a d become apparent from a consideration of the cokes r h r carbonaceous pr d t a be descriptive portion to follow, used, the catalyst support which we prefer to According to the present invention it has been use comprises a calcined diatomaceous earth. discovered that oleflns may be directly hydrated This ma a W e t. has g d a Dt V Y to the corresponding alcohols by continuously for ph p c ac Solutions a f is passing a gaseous mixture of the olefin and stable in the sense of being resistant to chemical water vapor at elevated temperatures and presattack and physical deterioration even with sures through a catalyst bed comprising a solid dong-continued usage. A particularly useful porous support which is incompletely saturated calcined diatomaceous earth product is that with a solution of phosphoric acid and which manufactured by the Johns-Manville Corporais substantially free of any seepage of the acid tion and marketed under the trade name solution, the activity of the bed being main- Celite, the grade thereof which preferably is tained at a high level for long periods of time used in the process of this invention being Celite by the addition of a solution of free phosphoric VIII. The latter material is available in small acid to the bed to make up for the acid lost 56 pellet form and has the composition,

present invention that the phosphoric acid-impregnated condition (that is, free of any substantial seepage of the phosphoric acid solution) during the hydration operation. Consequently, portant to bring the unit up to operating conditions in the proper manner and to thereafter add additional quantities of refresher acid, as required, in such a fashion as to permit the catalyst bed to be maintained in the dry condition during substantially the entire olefin hydration period.

The preferred method of initiating the ethylene hydration process, and of placing the apparatus on stream, is to' first impregnate the Celite Or other solid supporting material with an aqueous phosphoric acid solution having a strength of somewhat less than 70% (e. g.,

about 55-65%), with the acid being concentrated in situ on" the support as the catalyst bed is brought up to reaction temperature and operating conditions are established in the system. In this method of starting up the unit, the solid absorbent is preferably impregnated with the relatively dilute acid solution until the saturation point is reached. -The acid may be either hot or cold, and, in either condition, is preferably left in contact with the support for a period of at least one-half hour. The excess solution, if any, is then allowed to drain from the solid absorbent, whereupon the latter, if not already in place in the reactor vesselfis-placed therein in the desired position of support. The catalyst bed is then brought up to a temperature which may be somewhat below the operating temperature by passing a heated gas therethrough, as by recycling heated ethylene gas through the system under pressure, either with or without added water vapor, until the temperature in the bed reaches about 175 C. to 200 C. Once such a temperature is attained, water vapor, if not already present in the recycle stream, is gradually admixed with the ethylene, and with continued rise in the recycle stream and bed temperatures, increasingly large proportions of steam are employed until the desired operating pressure and ratio of steam to ethylene required for maintaining an acid concentration of 70% or above are established by the time the bed reaches an operating temperature between 275- 310 C. The unit is then ready to go on stream,

and the liquid obtained on passing the gaseous eflluent from the catalyst bed through a condenser is then sent to the ethanol extraction portions of the system instead of being discarded aswaste, as during the start-up period.

Heating the catalyst bed and bringing the unit on stream according to the method described in the preceding paragraph has the effect of concentrating the absorbed acid in situ on the support, with the result that there is obtained a catalyst bed which isincompletely saturated with an aqueous solution of phosphoric acid having a strength of 70% or more, and which manifests the dry condition to be it is 1111-- the practice of this invention. That is to say, the bed is either entirely free of acid seepage,

* or experiences extremely small and inconsequencatalyst bedis maintained in the dry tial seepage losses not at all like those encountered when the bed is maintained in the fully saturated condition. Furthermore, once the process is inoperation, the operating conditions are continuously so regulated as to maintain the relatively high acid concentration and" keep the bed in the dry state as the hydration operation continues, information as to representative operating conditions commensurate with this result being presented in the paragraph to fol- 10w- 3 As illustrated by the various curves appearing on the graph in the attached drawing, a given concentration of phosphoric acid may be attained at any given temperature by using any one of many combinations of pressures and water vapor-ethylene molar ratios. Curve 1 indicates the respective pressures and molar ratios to ;be employed if the phosphoric acid in the catalyst bed is to be maintained at a concentration of 75% and at a temperature of 300 C., water vapor-ethylene molar ratios of 0.75, 1.0 and 1.5, for example, being used with total system pressures of 1500, and 1180 and 950 pounds per square inch, respectively. Curve II also represents a system wherein the phosphoric acid is maintained at 75% but here the reaction, or

bed temperature, is reduced to 280 C., and under these conditions use of water vapor-ethylene molar ratios of 0.65, 1.0 and 1.5, for example,

requires the establishment of total system pressures of 1200, 875 and 700 pounds per square inch, respectively. In the system illustrated by curve 111 the conditions are such that the phosphoric acid attains a concentration of 85% at a reaction temperature of 300 C., and by inspecting that curve appropriate pressure and water Y vapor-ethylene molar ratios may be determined.

In curve IV the reaction temperature is reduced to 280 C. while maintaining the concentration of phosphoric acid at 85%, and again inspection of tlie curve will indicate proper operating conditions. The exact shape which the curve must assume for any given acid concentration and operating temperature may be calculated from known equilibrium data, though it is believed that inspection of the graph shown in the drawing will suggest appropriate operating conditions to be observed when acid concentrations between and and reaction temperatures between 280 C. and 300 C., are to'be established.

While the start-up method described above (involving impregnating the catalyst support with relatively dilute phosphoric acid and con centrating the latter in situ on the support as the catalystbed is brought up to operating temperatures) comprises the preferred method for initiating the olefin hydration process of the present invention, it is also possible to initially impregnate the bed with phosphoric acid having a concentration of 70% or more. This method has the disadvantage of entailing considerable weeping of acid from the bed as the latter is brought up to operating conditions unless extreme care is taken in the proportioning of the aqueous and non-aqueous components of the recycle mixture employed to heat the bed. Further, in these cases where the bed has been inititially saturated with the concentrated acid, weeping of acid from th'ebed is apt to occur for observed in I some little period after the unit has been placed s i on stream, though eventually the acid will be depleted to such an extent that the bed will assume the dry condition desired, and the process will then go on in the proper manner., Such cur in subsequently encountered portions of the apparatus with which the acid comes into contact.

Once the ethylene or other olefin hydration process is under way, it has been found that the activity of the catalyst bed is gradually reduced. This decrease in the eillciency of the bed is evidently attributable to losses of phosphoric acid therefrom in a manner not as yet fully understood since there is substantially no physical entrainment of phosphoric acid by the reactant gases passing through the catalyst bed. It therefore forms an important feature of the present invention that the activity oi the catalyst bed can be maintained at a relatively high and constant level without interruption of the hydration operation by addingfurther quantities of phosphoric acid to the bed to make up for the amount of acid lost therefrom as the process is continued.

By adding refresher acid in this manner, it'has been found that given units may be kept in continuous operation at high eillciency levels for periods of many months duration, whereas without the addition of new acid the etlleiency of the process would fall oil to such an extent that the process would be impractical of operation after,

6 l tively dilute (e. g., 65%). However, the preferred method of adding the refresher acid, even when the latter is supplied to the bed in an intermittent manner, is to so control the amount and rate of its addition as to prevent seepage of acid from the bed. In the case of either continuous or in-' termittent addition of the refresher acid, the latter may simply be allowed to drip into the catalyst bed, or it may be applied thereto in the form of a light spray. At the elevated temperatures prevailing in the system, any acid added is rapidly bro'ught'to the concentration of the acid already present. Accordingly, the concentration of acid added to the bed as the process continues ,is not significant, and as long as the amount mended, and particularly above 325 C., the overat most, a few weeks. The amount of refresher acid to be added is, in general, related to the quantity of alcohol produced. Thus, in the case where ethylene is the oleflnic reactant, the activity of the catalyst bed may be maintained at a high level by adding approximately 1 pound of phosphoric acid (calculated as 100% HJPOi) for every 150-250 pounds of ethanol produced. The addition of even smaller amounts of acid than this, e. g., of 1 pound of acid for every 400 pounds of ethanol, also exerts a beneficial eifect on the activity of the bed, though under these circumstances there will usually be experienced an overall downward drift in bed activity. Again, larger proportionate amounts of acid may also be employed in some plants, without harmfulresults. Thus, in some cases it has been found possible to add as much as one pound of HaPO4 per 100 pounds of ethanol produced, though here it was evident that flooding of the bed was occurring in some instances, with the resultant disadvantages of corrosion and fouling as noted above.

The refresher acid may be added to the catalyst bed ineither a continuous or an intermittent manner, though excellent results have been obtained by making periodic additions of the acid whenever-the eiliciency of the unit drops oil from about 5 to 20%. In either case, the amount of acid added, and the rate of its addition, should preferably be so controlled as to prevent substantially all seepage of acid therefrom. In the case of intermittent addition of refresher acid it is possible to operate the process by adding acid to the bed until some seepage of acid from the bed actually occurs before acid addition is terminated, for with continued operation the bed is quickly restored to the dry condition; this is particularly the case when the refresher acid is relaall efficiency of the operation is greatly impaired; not only is there a fall in the percentage of ethylene converted into ethyl alcohol per pass through. the catalyst, but also much 01' the ethylene is either converted into the polymer form or contributes to the formation of other products of an undesirable nature which, along with the polymenare diflicult to separate from the alcohol. Similarly, at lower temperatures than those here recommended, and particularly when the bed temperature begins to fall below 265 C., the proportion of ethylene converted to alcohol again falls off to such an extent that the process becomes impractical of operation.

The pressure to be maintained in the system when hydrating ethylene, and the water vaporethylene mole ratios to be observed for selected temperatures, acid concentrations and pressures, may be determined by resort to the graph presented in the attached drawing, or thesame may be calculated from available equilibrium data.

When olefins other than ethylene are being hydrated, the reaction temperatures (and pressures) are preferably somewhat lower than for ethylene. Thus, in the case of propylene good results are obtained by operating at about 200-250 C., while somewhat lower temperatures still are preferably employed with the higher olefins.

The ethylene employed as feed stock in the process of this invention may be derived from any convenient source, as by the catalytic cracking or thremal cracking of petroleum hydrocarbons. By whatever manner obtained, the ethylene is normally submitted to a scrubbing or other appropriate treatment to remove any other gases which maye be present. When manufacturing ethylene on a commercial scale, however, it is difllcult to remove all traces of such other gases as may be present, and as a result some are still present in the ethylene feed stock. While most of these gaseous impurities do not interfere with the hydration process, acetylene, which frequently is present in the ethylene in amounts of 1% or more, does not fall into this category. We have found that if either the ethylene or the water vapor admixed therewith, or even the feed water from which said vapor is produced, comes into contact with copper surfaces at one or more gaseous stream, the acetylene is readily converted to acetaldehyde as the gases pass through the catalyst bed, and no precautions need be taken when handling the eiliuent stream as regards cuprene formation. The term copper, as employed herein, refers not only to pure copper, but

are passed through the .also to those metals containing substantial amounts of copper, as 10% or more.

The following examples illustrate the manner in which the invention described herein may be practiced:

Example I Approximately 2.5 cubic feet (90 pounds) of Celite VIII pellets, each having a generally cylindrical shape and measuring g xfi inches, were placed in a copper-lined, steel reactor vessel where they were flooded with a cold aqueous solution of phosphoric acid (65%) for 2 hours. The acid was then drained from the pellets and they were allowed to stand for a further period of 2 hours. The bed was then found to contain '77 pounds of the acid solution, or 50 pounds of the acid expressed as 100% H3PO Ethylene was then charged into the system and the latter was brought up to a pressure of 865 pounds per square inch. The ethylene was then recycled through the system, at gradually in-' creasing temperatures, at the rate .of about 50 cubic feet per minute (standard conditions) until the catalyst bed reached'a temperature of 175 C. to 200 0., a period of about 1 hour being used to effect this phase of the drying operation. Small amounts of steam were then admixed with the ethylene recycle'strearrr, and with gradually increasing temperatures,'the proportion of water to ethylene was increased until the bed tem-. perature reached approximately 280 C., at which oint the desired operating water vapor-ethylene molar ratio of 0.6 has been established in the inlet stream. The rate of passage of combined gases over the catalyst was then raised to '75 cubic feet per minute and the temperature of the catalyst bed was gradually increased until it reached the operating temperature of 290 C.,.

this second phase ofthe heating cycle having taken another period of about an hour. At this point the acid on the bed had a strength of about 85%. It should be noted that during the foregoin heating operation, the gases coming out of the catalyst bed were passed through a condenser to effect separation of the ethylene and other normally gaseous materials from the water and other liquids formed during the condensation step. The gas phase was then recycled to the reactor after being heated and mixed with any desired quantities of steam. Once the system was in operation at 290 C., analysis of the liquid obtained by condensing the eilluent gases disclosed that 4.5% of the ethylene in the feed was being converted to ethanol per pass through the catalyst bed. At this point in the operation, the unit was regarded as being on stream,,and the liquid phase obtained in the condenser was sent to product recovery instead of being discarded as waste'as during the startup period. The process was then continued without interruption for a period of 300 hours. On then testing the condensate it was found that the percentage. of ethylene converted to ethanol per pass through the bed had been reduced to 3.9%. At this stage in the operation (the process being. meanwhile continued without interrup tion)", phosphoric acid was sprayed onto the catalyst bed at a rate equivalent to 8 pounds of 100% acid per day, though the acid added was actually in theform of a 65% aqueous solution. At the end of the third day, when approximately 24 pounds'of acid had been added (or an average of 1 pound-for each 200 pounds of alcohol theretofore produced), it was found that the activity of the catalyst bed had been substantially restored to the lever prevailing at the beginning of the run. Spraying of acid into the bed at the relatively slow rate mentioned above did not cause any weeping of acid from the bed, the latter seeming to retain its dry appearance, with all the refresher acid. added being rapidlybrought to a concentration of about 85%. Examination of the catalyst material on the completion of the run disclosed it to be in perfect condition, and there was no reason why the operation might not have been continued indefinitely at a high level of efficiency, with either periodic or continuous additions of the acid being made. The walls of the reactor vessel lying adjacent the catalyst bed exhibited little evidence of corrosion.

Example I! I Approximately 0.5 cubic foot of Celite VIII pellets was immersed for 2 hours in a 63% aquesel, where they were dried and the phosphoric acid concentrated to a strength of 80% to 85% by first recycling heated ethylene, and thereafter ethylene and water vapor, through the bed in the manner described in Example I. This cat- I alyst was kept in continuousoperation for 3454 hours, operating with a total system pressure of 915 pounds per square inch, a bed temperature between 294 C. and 300 C., a water vapor-ethylene molar ratio of from 0.56 to 0.64, and with from 15 to 20 cubic feet of reactant. gases being passed through the catalyst bed per minute. During the first 2514 hours of this run, occasional additions of dilute phosphoric acid were made, the amount added in no case being sufficient to cause seepage of acid from the catalyst bed, butno attempt was made to maintain the conversion at peak efliciency. At the end of said 2514-hour period, and when the bed contained an undetermined amount of phosphoric acid of to strength, approximately 3.2% of the ethylene in the bed was being converted to ethanol per pass through the catalyst bed. The addition of 2.15 pounds'of onto the bed in the form of a 39.7% aqueous solution at the rate of about 45 milliliters per hour, raised the ethylene conversion to 4.4%. During the succeeding portion of the run, six further additions of the acid were made, or one about every 130 hours, the conversion of ethylene acid HaPO4), sprayed the addition in each case being made in substantially the form and manner described above. During the last 940 hours of the run, in which time all seven of the acid additions here de-' scribed were made, an average of 384 pounds of alcohol were produced for each pound of acid added. When the equipment employed in this example was disassembled after being in operation for 3454 hours, the reactor vessel exhibited little evidence of corrosion, and it appeared that there had been no seepage of acid from the bed at any time during the run. Further, the pellets comprising the support in the catalyst bed were in excellent condition. It seemed evident that the process could have been continued more or less indefinitely,

Example III This operation was directed to the production of isopropanol. The catalyst employed was prepared by immersing Celite VIII pellets for approximately 2 hours in a boiling, aqueous solution of H PO4 (60%), and thereafter draining the pellets and drying them in a stream of air at 120 C. for 18 hours. The resulting pellets, which contained 43.1% by weight of acid (calculated as 100% H3PO4) and presented a dry appearance, were then placed in a reactor tube. The gaseous feed mixtureflnade up of propylene and water vapor (H2O/C3Hs mol ratio=0.62), was then passed through the reactor tube for 33.6 hours (approximately 6.7 hrs. per day) at temperatures of from about 225 to 250 C., a pressure of 550 p. s. i. g. and a vapor space velocity per minute of about 40 (calculated at 60 F. and 1 atmosphere). The gaseous eflluent from the reactor tube was passed through a condenser, and the resulting condensate was found to contain an average of 21.1% isopropanol, with the average conversion of feed propylene to isopropanol per pass through the reaction tube being 3.8%. At the end of this run the activity of the catalyst was found to be substantially undiminished, though, as the process is continued still further, the activity of the catalyst is gradually impaired. However, the activity of the catalyst can be restored to its original (fresh) level whenever desired by providing the pellets with fresh quantitles of phosphoric acid in the amount of 1 pound of the acid (calculated as 100% HaPO4) for every 200 pounds of isopropanol produced.

Example IV This operation illustrates the manner in which the present invention is employed in the production of ethanol on a plant scale. Here the catalyst support in a given unit is made up of 39,000 pounds of the Celite VIII pellets described in Example I, these pellets forming a bed '7 feet in diameter and 27 feet thick when placed in a cylindrical, copper-lined, steel reactor vessel. This Celite bed is impregnated with phosphoric acid by thrice repeating the following sequence of steps: (1) need the bed with an aqueous solution of H3PO4 (65%), (2)allow the bed to soak in the acid solution at room temperatures for 3 hours; and (3) drain the acid from the bed and pump it out of the reactor vessel. The acid on the pellets is then concentrated to the desired operating strength of about 80-82% as the catalyst bed is brought up to operating temperature and the unit is placed on stream. This acidconcentrating and heating step is accomplished by pressuring the system with ethylene (500 and at a high level of efiiciency.

i p. s. i.) and then recycling the ethylene through the catalyst bed at an initial vapor space velocity per minute (VSVM) of approximately and at gradually increasing temperatures, the ethylene being passed through a condenser and a water scrubber after leaving the catalyst bed before being again heated and circulated through the catalyst-filled reaction chamber. In the earlier phases of the warm-up operation, no additional water vapor other than that provided by the water scrubber need be added to the recycle gases. The water in the scrubber is a 50 C. at the start of the heating cycle and builds up to about 65 C. as the recycle gases from the catalyst bed become hotter; however, to avoid operating difficulties, the temperature in the scrubber is thereafter maintained at 65 C. As the temperature in the catalyst bed (by which is meant the average or median temperature prevailing in the bed) rises above 65 C. and begins to approach 90-100 C., additional quantities of water or water vapor are admixed with the recycle gases in an amount sufiicient to provide a water partial pressure of approximately 6 p. s. i. in the system. The amounts of water vapor added to the recycle stream are then gradually increased as the bed temperature rises still further until, with the attainment of operating temperatures (290 C.), the mole ratio of water to ethylene in the gases fed to the catalyst bed is approximately 0.6. Thus, as the bed temperatures of 110, 140, 150, 190, 220 and 260 C. are achieved, the partial pressure of water established in the system is approximately 8.5, 17.5, 23.5, 57, 100, and 245 p. s. i., respectively. By adding the water in increasingly large amounts to the recycle stream in this manner, the phosphoric acid on the catalyst bed is gradually concentrated from its initial strength of 65% (which strength is maintained until the bed temperature reaches approximately -80 C. under the conditions described herein) to a strength of approximately -82% as operating conditions are established in the system. In bringing the bed up to operating temperatures in the manner here described, care is taken to increase the temperature of the recycle gases at such a rate that the spread in temperatures between the upper (inlet) and lower (outlet) portions of the bed does not exceed about 30 C. This requires a heating period of approximately 20-25 hrs. for the aforementioned catalyst bed. With the attainment of operating temperatures, the system is placed on stream by connecting the recycle feed line with. a source of ethylene under a pressure of 1,000 p. s. i. and by diverting the liquid formed in the condenser to the ethanol recovery portions of the plant instead of discarding the condensate as waste. The unit is thereafter maintained in continuous operation, utilizing a VSVM rate of 30 as well as a water/ethylene mole ratio in the feed gas of approximately 0.6. It may be noted that the non-aqueous component of the gaseous feed stream supplied the catalyst bed contains approximately ethylene. Under these conditions, approximately 4.2% of the ethylene in the feed is converted to ethanol per pass through the catalyst bed. This conversion rate falls off by approximately 10% as the process is continued for hours, during which period there is produced approximately 430,000 pounds of ethanol. During the next 100 hours of operation (in which a further quantity of 430,000 pounds of ethanol is produced) the refresher acid (65% aqueous HsPO4) is continuously sprayed onto the bed.

' produced during the 200 hour period of operation.

The addition of refresher acid in the i'cregoing manner has the efieet oi restoring the activity of the catalyst bed to its original level, while at the same time being insuflicient to cause any appreciable weeping oi! acid from the bed. The process is then continued employing the same pattern of, approximately 100 hours of operation without addition of refresher acid followed by a like period during which acid is sprayed onto the bed.

Example V The process of the foregoing example is repeated except that here the catalyst bed is brought up to operating temperature in.the following manner: Heated ethylene gas, which is tree of any water vapor other than that provided by the scrubber, is passed through the catalyst bed until the latter reaches a temperature or approximately 190 C., the time required for this portion of the heating step being about hours. As the catalyst bed is thenheated above 190 C., water vapor is added to the ethylene recycle stream, and in increasingly large amounts, until, with the attainment o! a bed temperature of about 290 C'. (requiring a further heating period of about 1 hours) the desired H2O/C2Hs teed ratio of 0.6 is established.

The invention claimed is:

1. In a process for the continuous production of ethyl alcohol, the steps comprising preparing a catalyst bed by impregnating a solid, porous supporting material with phosphoric acid a! strength less than 70% and drying said support to concentrate the acid absorbed thereby to a strength between 75% and 85%, continuously passing a gaseous mixture of ethylene and water vapor through the catalyst bed at a temperature sufilcient to maintain the .bed at a temperature between 290 C. and 300 C. while simultaneously so controlling the pressure or said mixture and the water vapor to ethylene molar ratio therein as to maintain the strength of the absorbed acid between 75% and 85%; and adding further amounts of phosphoric acid to said bed as the process continues, said last named acid being added as an aqueous solution of tree phosphoric acid in the amount of about one pound of acid (calculated as 100% H3PO4) for each 100 to 400 pounds or alcohol produced during the process, and at a rate so controlled as to prevent substantially all seepage of acid from the bed.

2. In a process for the continuous production or ethyl alcohol, the steps comprising preparing a catalyst bed by impregnating asolid, porous supporting material with phosphoric acid of strength less than 70% and drying said support to concentrate the acid absorbed thereby to a strength of at least 75%; continuously passing a gaseous mixture of ethylene and water vapor through the catalyst bed at a temperature sufflcient to maintain the bed at a temperature between 270 C. and 310 C., while so controlling the pressure of said mixture and the relative proportions or its ethylene and water vapor components as to maintain the acid at a strength of at least 75%; and adding a solution of tree phosphoric acid to the bed as the process continues, but only in a quantity sufllcient to replace acid lost as a result of the passage of said mixture through the bed. the rate of addition or said further amount! of phosphoric acid being so'controlled as to preggriit substantially all seepage or acid'trom the g 3. The process of claim 2 wherein said solid, porous supporting material is made up 01 small pellets oi calcined diatomaceous earth.

4. In a process for producing ethyl alcohol by the hydration of ethylene, the steps comprising absorbing phosphoric acid or less than 70% strength on a solid, porous support; dryin said support to increase the concentration of the absorbed acid thereon to at least 75%; continuously bringing a mixture or ethylene andwater vapor into intimate contact with said support and the concentrated acid absorbed thereon at a temperature between 270C. and 310 C. and under such conditions of elevated pressure and proportions of water vapor to ethylene as to maintain the concentration of said acid above 75% and continuously adding an aqueous solution of tree phosphoric acid to the support in an amount equivalent to about one pound of 100% HaPOs for each 100 to 400 pounds of alcohol produced ata rate controlled so as to prevent seepage oi acid solution from the support. I

5. The process or claim 4 wherein said solid, porous support is made up of small pellets oi calcined diatomaceous earth.

6. In a process for producing ethyl alcohol by the hydration of ethylene, the steps comprising continuously passing a gaseous mixture. or ethylene and water vapor, at elevated temperature and pressure, into intimate contact with a catalyst bed made up of a solid, porous support containing absorbed phosphoric acid of strength greater than 70%,said acid having been supplied to said support in a more dilute form and thereafter having beenconcentrated in situ on said support; maintaining the activity of the catalyst bed at a high level as the process is continued by the addition of quantities of phosphoric acid in the form of an aqueous solution or the free acid to 'said support, said acid being added only in an amount suflicient to replace acid lost on passing said mixture into contact with said catalyst and a rate so controlled as to prevent substantially all seepage or acid from the support; and so controlling the temperature, pressure and proportion of ethylene to water vapor in said mixture as to maintain the concentration of acid absorbed on said catalyst. including that added during continuation of the process, above 70% 7. The process of claim 6 wherein the acid addin the amount of 1 pound (calculated as 100% 8. In a process for producing ethyl alcohol whereby a gaseous mixture of ethylene and water vapor, at elevated temperature and pressure, is continuously passed through a catalyst bed com.- prising phosphoric acid absorbed within a solid, porous support, which bed is free or any seepage of phosphoric acid, the step comprising adding a, solution of free phosphoric acid to the support to make up for the amount of said acid lost therefrom as a result of passing said gaseous mixture through the catalyst bed, the amount or said make-up acid added to the support and the rate of its addition thereto being so controlled as to prevent substantially all seepage of acid from the support.

9. The process of claim 8 wherein the-amount 75 of make-up phosphoric acid added to the support ed during continuation or the process is provided is approximately one pound (calculated as 100% M04) for each 100 to 400 pounds of alcohol produced.

10. In a process for producing alcohols by the direct hydration of olefins, the steps comprising absorbing a solution of phosphoric acid of less than 70% strength on a solid, porous support;

drying the acid-containing support to increase" the concentration of absorbed acid to at least 75%; continuously bringing a gaseous feed mixture of olefin and water into intimate contact with said concentrated acid-containing support at such elevated conditions of temperature and pressure, for the ratio 01 water to olefin employed in the feed mixture, as to maintain the phosphoric acid on the support at a concentration of at least 75%; and adding a solution of free phosphoric acid to the support, as the hydration operation continues, to maize up for the amount of phosphoric acid which is lost from the support as a result of passing the gaseous leed mixture therethrough. the amount of phosphoric acid added in this fashion not exceeding one pound (calculated as 100% H3PO4) for each 100 pounds of alcohol produced. 4

11. In a process for producing alcohols by the direct hydration of oleflns whereby a gaseous of phosphoric acid added in this fashion not exceeding one pound (calculated as HsPOi) for each 100 pounds of alcohol produced.

12. The process of claim 11 wherein the olefinic component of the feed mixture is ethylene and the alcohol produced is ethanol.

13. The process of claim 11 wherein the olefinic component of the feed mixture is propylene and the alcohol produced is ieopropanol.

CHARLES R. NELSON. MARION A. D. TAYLOR. DONALD D. DAVIDSON. LESLIE M. PETERS.

No references cited. 

11. IN A PROCESS FOR PRODUCING ALCOHOLS BY THE DIRECT HYDRATION OF OLEFINS WHEREBY A GASEOUS MIXTURE OF OLEFIN AND WATER VAPOR, AT ELEVATED TEMPERATURE AND PRESSURE, IS CONTINUOUSLY PASSED THROUGH A CATALYST BED COMPRISING PHOSPHORIC ACID ABSORBED WITHIN A SOLID POROUS SUPPORT, WHICH BED IS FREE OF SUBSTANTIALLY ALL SEEPAGE OF PHOSPHORIC ACID, THE STEP COMPRISING ADDING A SOLUTION OF FREE PHOSPHORIC ACID TO THE SUPPORT AS THE HYDRATION OPERATION CONTINUES, TO MAKE UP FOR THE AMOUNT OF PHOSPHORIC ACID WHICH IS LOST FROM THE SUPPORT AS A RESULT OF PASSING THE GASEOUS FEED MIXTURE THERETHROUGH, THE AMOUNT OF PHOSPHORIC ACID ADDED IN THIS FASHION NOT EXCEEDING ONE POUND (CALCULATED AS 100% H3PO4) FOR EACH 100 POUNDS OF ALCOHOL PRODUCED. 